U.S. patent number 11,352,290 [Application Number 16/620,307] was granted by the patent office on 2022-06-07 for transparent .beta.-quartz glass-ceramics with low lithium content.
This patent grant is currently assigned to EUROKERA. The grantee listed for this patent is Eurokera. Invention is credited to Marie Comte, Philippe Lehuede, Thiphaine Ogier.
United States Patent |
11,352,290 |
Comte , et al. |
June 7, 2022 |
Transparent .beta.-quartz glass-ceramics with low lithium
content
Abstract
The present application provides transparent glass-ceramics of
.beta.-quartz of composition containing a small content of lithium,
articles constituted at least in part of said glass-ceramics,
glasses precursors of said glass-ceramics, and also a method of
preparing said articles. Said glass-ceramics have a composition,
free of arsenic oxide and antimony oxide, except for inevitable
traces, expressed as percentages by weight of oxides, containing:
62% to 68% of SiO.sub.2; 17% to 21% of AI.sub.2O.sub.3; 1% to
<2% of Li.sub.2O; 1% to 4% of MgO; 1% to 6% of ZnO; 0 to 4% of
BaO; 0 to 4% of SrO; 0 to 1% of CaO; 1% to 5% of TiO.sub.2; 0 to 2%
of ZrO.sub.2; 0 to 1% of Na.sub.2O; 0 to 1% of K.sub.2O; with
Na.sub.2O+K.sub.2O+BaO+SrO+CaO<6%; optionally up to 2% of at
least one fining agent comprising SnO.sub.2; and optionally up to
2% of at least one coloring agent.
Inventors: |
Comte; Marie (Fontenay aux
Roses, FR), Ogier; Thiphaine (Paris, FR),
Lehuede; Philippe (Dammarie les Lys, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Eurokera |
Jouarre |
N/A |
FR |
|
|
Assignee: |
EUROKERA (Jouarre,
FR)
|
Family
ID: |
1000006355441 |
Appl.
No.: |
16/620,307 |
Filed: |
June 6, 2018 |
PCT
Filed: |
June 06, 2018 |
PCT No.: |
PCT/EP2018/064909 |
371(c)(1),(2),(4) Date: |
December 06, 2019 |
PCT
Pub. No.: |
WO2018/224554 |
PCT
Pub. Date: |
December 13, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20200189965 A1 |
Jun 18, 2020 |
|
Foreign Application Priority Data
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C03C
1/04 (20130101); C03C 4/02 (20130101); C03C
10/0009 (20130101); C03C 3/085 (20130101); C03C
3/087 (20130101); C03C 2204/00 (20130101); C03B
32/02 (20130101) |
Current International
Class: |
C03C
10/00 (20060101); C03C 3/085 (20060101); C03C
4/02 (20060101); C03C 1/04 (20060101); C03C
3/087 (20060101); C03B 32/02 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
104350017 |
|
Feb 2015 |
|
CN |
|
104936914 |
|
Sep 2015 |
|
CN |
|
2887871 |
|
Jan 2007 |
|
FR |
|
30200359 |
|
Oct 2015 |
|
FR |
|
2006-330010 |
|
Dec 2006 |
|
JP |
|
WO2005010574 |
|
Feb 2005 |
|
WO |
|
Other References
International Search Report & Written Opinion relating to
International Application No. PCT/EP2018/064909. cited by applicant
.
China First Office Action issued in China Application No.
201880038161.6 dated Oct. 21, 2021. cited by applicant.
|
Primary Examiner: Group; Karl E
Assistant Examiner: Miller; Cameron K
Attorney, Agent or Firm: Dinsmore & Shohl LLP
Claims
The invention claimed is:
1. A transparent glass-ceramic containing a solid solution of
.beta.-quartz as its main crystalline phase, the composition of
which, free of arsenic oxide and antimony oxide, except for
inevitable traces, expressed as percentages by weight of oxides,
comprises: 62% to 68% of SiO.sub.2; 17% to 21% of Al.sub.2O.sub.3;
1% to <2% of Li.sub.2O; 1% to 4% of MgO; 1% to 6% of ZnO; 0 to
4% of BaO; 0 to 4% of SrO; 0 to 1% of CaO; 1% to 5% of TiO.sub.2; 0
to 2% of ZrO.sub.2; 0 to 1% of Na.sub.2O; 0 to 1% of K.sub.2O; with
Na.sub.2O+K.sub.2O+BaO+SrO+CaO.ltoreq.6%; optionally up to 2% of at
least one fining agent comprising SnO.sub.2; and 0.01% to 2% of at
least one coloring agent, wherein the coloring agent comprises
0.005% to 0.1% V.sub.2O.sub.5 mixed with at least one other
coloring agent selected from CoO, Cr.sub.2O.sub.3, and
Fe.sub.2O.sub.3; wherein the transparent glass ceramic comprises a
coefficient of thermal expansion CTE.sub.25.degree. C.-300.degree.
C. of less than 2010.sup.-7K.sup.-1; and the transparent glass
ceramic has a thickness from 1 mm to 8 mm and an integrated
transmission of less than 10% while maintaining transmission at 625
nm greater than 1% and at 950 nm from 50% to 75%.
2. The glass-ceramic according to claim 1, wherein the composition
comprises 1% to 1.9% of Li.sub.2O.
3. The glass-ceramic according to claim 1, wherein the composition
comprises 17.5% to 19% of Al.sub.2O.sub.3.
4. The glass-ceramic according to claim 1 wherein the composition
comprises 1% to 3% of MgO.
5. The glass-ceramic according to claim 1, wherein the composition
comprises 1% to 4% of ZnO.
6. The glass-ceramic according to claim 1, wherein the composition
comprises ZrO.sub.2.
7. The glass-ceramic according to claim 1, wherein the composition
comprises 0.05% to 0.6% of SnO.sub.2.
8. An article constituted, at least in part, of a glass-ceramic
according to claim 1.
9. A method of preparing an article constituted, at least in part,
of a glass-ceramic containing a solid solution of .beta.-quartz as
its main crystalline phase, comprising in succession: melting a
charge of raw materials able to vitrify, followed by fining the
resulting molten glass; cooling the resulting fined molten glass
and simultaneously shaping it to the shape desired for the intended
article; and applying ceramming heat treatment to said shaped
glass; wherein said charge has a composition that makes it possible
to obtain the transparent glass-ceramic, the composition of which,
free of arsenic oxide and antimony oxide, except for inevitable
traces, expressed as percentages by weight of oxides, comprises:
62% to 68% of SiO.sub.2; 17% to 21% of Al.sub.2O.sub.3; 1% to
<2% of Li.sub.2O; 1% to 4% of MgO; 1% to 6% of ZnO; 0 to 4% of
BaO; 0 to 4% of SrO; 0 to 1% of CaO; 1% to 5% of TiO.sub.2; 0 to 2%
of ZrO.sub.2; 0 to 1% of Na.sub.2O; 0 to 1% of K.sub.2O; with
Na.sub.2O+K.sub.2O+BaO+SrO+CaO.ltoreq.6%; 0 to 2% of at least one
fining agent comprising SnO.sub.2; and 0.01% to 2% of at least one
coloring agent, wherein the coloring agent comprises 0.005% to 0.1%
V.sub.2O.sub.5 mixed with at least one other coloring agent
selected from CoO, Cr.sub.2O.sub.3, and Fe.sub.2O.sub.3, wherein
the transparent glass ceramic comprises a coefficient of thermal
expansion CTE.sub.25.degree. C.-300.degree. C. of less than
2010.sup.-7K.sup.-1, the transparent glass ceramic having a
thickness from 1 mm to 8 mm and an integrated transmission of less
than 10% while maintaining transmission at 625 nm greater than 1%
and at 950 nm from 50% to 75%.
10. The method according to claim 9, wherein said charge of raw
materials able to vitrify, free of As.sub.2O.sub.3 and
Sb.sub.2O.sub.3, except for inevitable traces, contains SnO.sub.2
as fining agent.
11. The method of claim 10, wherein the charge of raw materials
able to vitrify, free of As.sub.2O.sub.3 and Sb.sub.2O.sub.3,
except for inevitable traces, comprises 0.05% to 0.6% of
SnO.sub.2.
12. The glass-ceramic according to claim 2, wherein the composition
comprises 1.5% to 1.9% of Li.sub.2O.
13. The glass-ceramic of claim 5, wherein the composition comprises
3% to 4% of ZnO.
14. The glass-ceramic according to claim 6, wherein the composition
0.5% to 2% of ZrO.sub.2.
15. The glass-ceramic according to claim 6, wherein the composition
1% to 2% of ZrO.sub.2.
16. The glass-ceramic according to claim 7, wherein the composition
comprises 0.15% to 0.4% of SnO.sub.2.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority under 35 U.S.C
.sctn. 365 of International Patent Application Serial No.
PCT/EP2018/064909 filed on Jun. 6, 2018 designating the United
States of America, the content of which is relied upon and
incorporated herein by reference in its entirety, which in turn
claims the benefit of priority under 35 U.S.C. .sctn. 119 of French
Patent Application Serial No. 1755049 filed on Jun. 7, 2017, the
content of which is relied upon and incorporated herein by
reference in its entirety.
The context of the present application is that of transparent low
expansion glass-ceramics containing a solid solution of
.beta.-quartz as the main crystalline phase. The present
application relates more particularly to: transparent
glass-ceramics containing a solid solution of .beta.-quartz as the
main crystalline phase and a composition with a low lithium
content; articles constituted at least in part of these
glass-ceramics; aluminosilicate glasses, precursors of these
glass-ceramics; and a method of preparing these articles.
Transparent glass-ceramics of the lithium aluminosilicate (LAS)
type containing a solid solution of .beta.-quartz as the main
crystalline phase have been in existence for more than 20 years.
They are described in numerous patent documents and in particular
in U.S. Pat. No. 5,070,045 and patent application WO 2012/156444.
They are used in particular appliances as the material for
constituting cooktops, cooking utensils, microwave oven plates,
fireplace windows, fireplace inserts, stove windows, oven doors (in
particular for pyrolytic and catalytic oven), and fire-windows.
In order to obtain such glass-ceramics (and more precisely in order
to eliminate inclusions of gas within the precursor molten glass),
conventional fining agents, As.sub.2O.sub.3 and/or Sb.sub.2O.sub.3,
have been in use for a long time. Given the toxicity of these two
elements and the ever more severe regulations that are in force, it
is desirable to avoid using these (toxic) fining agents in the
fabrication of the precursor glass. SnO.sub.2 has been proposed as
a substitute fining agent (see in particular the teaching of patent
documents U.S. Pat. Nos. 6,846,760, 8,053,381, and WO 2012/156444).
It is being used more and more. Nevertheless, at a similar fining
temperature, it is found to be less effective than As.sub.2O.sub.3.
In general manner, and particularly in the context of using
SnO.sub.2 as a fining agent, in order to facilitate fining, it is
advantageous to have (precursor) glasses that have low viscosities
at high temperature.
Depending on the heating means that are associated with cooktops
used (radiant heating means or induction heating means),
requirements concerning values for the (linear) coefficient of
thermal expansion (CTE) of the material constituting said cooktops
are more or less constraining. Cooktops used with radiant heaters
may be raised to temperatures as high as 725.degree. C., and in
order to withstand the thermal shocks and the thermal gradients
that can arise in the cooktop, they have a CTE that generally lies
in the range -1010.sup.-7 per Kelvin (K.sup.-1) to
+1010.sup.-7K.sup.-1. Cooktops used with induction heaters are
subjected to lower temperatures (at most about 400.degree. C.). A
new generation of inductors, using infrared sensors, has also
recently appeared. Those sensors make it possible for the
temperature of the cooktops to be better controlled and not to
exceed 300.degree. C. Cooktops used with induction heaters are
therefore subjected to thermal shocks that are less violent; the
CTE of said cooktops can therefore be greater.
For reasons of appearance, it is also desirable for a cooktop, even
when transparent, to mask the elements that are placed beneath it,
such as induction coils, electric wiring, and circuits for
controlling and monitoring the cooking appliance. An opacifier may
be deposited on the bottom face of such a cooktop or the material
from which it is constituted may be strongly colored. If colored,
some minimum level of transmission must nevertheless be conserved
so that displays can be seen, e.g. as a result of light emitted by
light-emitting diodes (LEDs) placed under the plate.
Lithium is one of the main ingredients of glass-ceramics (of the
lithium aluminosilicate (LAS) type containing a solid solution of
.beta.-quartz as the main crystalline phase). At present, lithium
is present in the composition of said glass-ceramics, generally at
contents lying in the range 2.5% to 4.5%, and more generally
contents in the range 3.6% to 4.0% by weight (expressed in terms of
Li.sub.2O), essentially as an ingredient of the solid solution of
.beta.-quartz and as a flux for the glass. At present, the supply
of lithium is less reliable than it used to be. In any event, this
element is becoming more expensive. The reason for this recent
pressure on the availability and the price of lithium lies in the
increasing demand for lithium for producing lithium batteries.
The inventors have thus sought glass-ceramic compositions that show
high performance with a low lithium content. As a result of their
research, they have found compositions with lithium contents that
are considerably reduced compared with those of existing
glass-ceramics (see below).
The prior art already describes glasses and glass-ceramics having
compositions with various low contents of lithium. Thus: from
aluminosilicate glasses that do not contain lithium but rather a
high content of zinc, it is known that it is possible to obtain
glass-ceramics containing a .beta.-quartz solid solution as the
main crystalline phase. Nevertheless, such glass-ceramics are not
transparent (they are opaque), their precursor glasses have low
viscosity at the liquidus temperature, and the heat treatments
required for crystallizing (ceramming) said precursor glasses in
order to obtain said glass-ceramics are lengthy (see the book
"Glass-ceramic technology", 2.sup.nd edition, by W. Holland and G.
H. Beall, pp. 116-117 (Wiley 2012)); patent application US
2016/0174301 describes glasses having low CTE values
(CTE.sub.20-300.degree. C.<3010.sup.-7K.sup.-1), that can be
suitable material for making induction cooktops. Said glasses do
not contain alkalis in their composition. Consequently, they are
rather difficult to melt: firstly, they have high viscosities at
high temperature, and secondly they have high electrical
resistivities, so that very high voltages are needed to work them
in an electrically heated oven. Such glasses may be colored by
oxides of transition element, but the presence of such coloring
agents in those glasses can hinder melting them, by absorbing
infrared radiation; patent application WO 2005/010574 discloses
optical devices comprising microlenses. A part of the devices is
made of a crystallized glass, the disclosed composition of which is
broad. The CTE considered is CTE from -40 to 80.degree. C. The
teaching of said prior art document lies in a context far from the
one of the present application; patent application WO 2015/166183
(corresponding to patent application FR 3 020 359) describes
partially crystallized glass plates that are optionally transparent
and preferably not colored having CTE.sub.20-300.degree. C. values
lying in the range 2010.sup.-7K.sup.-1 to 4010.sup.-7K.sup.-1. That
document does not contain data showing that it is possible to
obtain materials having both the indicated compositions and
CTE.sub.20-300.degree. C. values that are lower than
2010.sup.-7K.sup.-1; neither does that document contain any data
about high-temperature viscosity. The compositions disclosed are
very broad; they may contain 1% to 2%, advantageously 1.2% to 1.8%,
preferably at most 1.5% by weight of Li.sub.2O; U.S. Pat. No.
9,446,982 describes colored transparent glass-ceramics containing a
solid solution of .beta.-quartz as the main crystalline phase and
having lithium contents (expressed as Li.sub.2O) in the range 2% to
less than 3% by weight (at least 2% by weight, with reference to
controlling crystallization). For the glass-ceramics described, and
with reference to the technical problem of making said
glass-ceramics compatible with them being decorated, it is desired
to obtain CTE.sub.ambient temperature--700.degree. C. values in the
range 1010.sup.-7K.sup.-1 to 2510.sup.-7K.sup.-1; patent
application US 2013/0085058 addresses fining glasses that are
precursors of lithium aluminosilicate (LAS) type glass-ceramics,
and more specifically avoiding reboiling within such glasses (the
only properties specified in the examples relate to suitability for
fining). Said glasses do not have more than 10 parts per million
(ppm) of sulfur (S) in their composition. Their composition, which
is free of As.sub.2O.sub.3 and of Sb.sub.2O.sub.3, may have 1% to
6% of Li.sub.2O. It does not contain coloring elements. The
compositions exemplified do not have ZnO, and for the most part
they have high contents of Li.sub.2O (3.5% and 4% by weight);
patent application EP 1 170 262 describes transparent
glass-ceramics of the lithium aluminosilicate (LAS) type suitable
for use as an optical waveguide element. The compositions specified
are broad; most of the example compositions have high contents of
Li.sub.2O and of Al.sub.2O.sub.3, together with low contents of
SiO.sub.2; and U.S. Pat. No. 9,018,113 describes colored
transparent glass-ceramics usable as cooktops associated with
induction heating. Their composition has 1.5% to 4.2% of Li.sub.2O;
the compositions exemplified have high contents of Li.sub.2O
(>2.9% by weight). No data is given about the high-temperature
viscosity of the precursor glasses.
In such a context, the inventors have investigated the potential
existence of transparent glass-ceramics, the composition of which
has a low lithium content (less than 2% by weight of Li.sub.2O (see
below)) and that are entirely suitable for use as the material for
making cooktops in a context of induction heating, and more
particularly in a context of induction heating using infrared
sensors for controlling heating (it is mentioned above that the
maximum temperature reached by a cooktop in operation is about
400.degree. C. (for induction heating in general) and does not
exceed 300.degree. C. (for induction heating with infrared
sensors)). Such glass-ceramics need to satisfy the following
specifications: being transparent (even if they are usually highly
colored): at the intended utilization thickness (plates typically 1
millimeter (mm) to 8 mm thick, more generally 2 mm to 5 mm thick,
and often 4 mm thick), said glass-ceramics need to have integrated
transmission, TL (%) equal to or greater than 1% and a diffusion
percentage less than 2%. Transmission measurements may be performed
using a spectrometer having an integrating sphere, by way of
example. On the basis of these measurements, the integrated
transmission (TL (%)) in the visible range (between 380 and 780 nm)
and the diffusion percentage (Diffusion (%)) are calculated using
the standard ASTM D 1003-13 (under D65 illuminant with 2.degree.
observer); having a CTE.sub.25-300.degree. C. lying in the range
+/-2510.sup.-7K.sup.-1
(-2510.sup.-7K.sup.-1.ltoreq.CTE.ltoreq.+2510.sup.-7K.sup.1) and
preferably in the range +/-2010.sup.-7K.sup.-1
(-2010.sup.-7K.sup.-1.ltoreq.CTE.ltoreq.+2010.sup.-7K.sup.-1), so
as to be acceptable for use with induction heater means, and more
particularly induction heater means associated with infrared
sensors (it has to be understood that said CTE is inferior or equal
to +2510.sup.-7K.sup.-1, advantageously inferior or equal to
+2010.sup.-7K.sup.-1, in the spirit of what has been specified
above about the teaching of the prior art), and having a precursor
glass that possesses advantageous properties, even the same
advantageous properties as the precursor glasses for prior art
glass-ceramics containing a higher content of Li.sub.2O; i.e.: said
precursor glass must have a low liquidus temperature
(<1400.degree. C.) and a high viscosity at the liquidus (greater
than 200 Pas, indeed greater than 400 Pas, preferably greater than
500 Pas), thereby facilitating forming; and/or, advantageously, and
said precursor glass must possess a low viscosity at high
temperature (T.sub.30 Pas<1640.degree. C.), thereby facilitating
fining.
In other respects it is highly appreciated for said precursor glass
to be capable of being transformed into glass-ceramic in a short
length of time (<3 hours (h)), and preferably in a very short
length of time (<1 h), and/or, advantageously and, to also have
an electrical resistivity, at a viscosity of 30 pascal seconds
(Pas), of less than 50 ohm centimeters (.OMEGA.cm) (preferably less
than 20 .OMEGA.cm). The man skilled in the art will understand (in
view of the composition of the glass-ceramics below stated) that
obtaining these two last properties, which are opportunely required
for the precursor glass, raises no particular difficulty.
It is also particularly interesting for the transparent
glass-ceramics aimed to have their composition free of
As.sub.2O.sub.3 and Sb.sub.2O.sub.3 (except for inevitable
traces).
The inventors have established that such glass-ceramics exist with
a composition that therefore contains little lithium (less than 2%
by weight of Li.sub.2O) and that satisfies the above
specifications. Said glass-ceramics constitute the first aspect of
the present application. In characteristic manner, these
glass-ceramics have the following composition, free of arsenic
oxide and antimony oxide, except for inevitable traces, expressed
in percentages by weight of oxides:
62% to 68% of SiO.sub.2;
17% to 21% of Al.sub.2O.sub.3;
1% to <2% of Li.sub.2O;
1% to 4% of MgO;
1% to 6% of ZnO;
0 to 4% of BaO;
0 to 4% of SrO;
0 to 1% of CaO;
1% to 5% of TiO.sub.2;
0 to 2% of ZrO.sub.2;
0 to 1% of Na.sub.2O;
0 to 1% of K.sub.2O;
with Na.sub.2O+K.sub.2O+BaO+SrO+CaO.ltoreq.6%;
optionally up to 2% of at least one fining agent comprising
SnO.sub.2; and
optionally up to 2% of at least one coloring agent.
The following may be specified concerning each of the ingredients
involved (or potentially involved) in the above-specified
composition at the specified contents (the extreme values of each
of the ranges specified (above and below) being included in said
ranges). SiO.sub.2 (62%-68%): the content of SiO.sub.2
(.gtoreq.62%) must be suitable for obtaining a precursor glass that
is sufficiently viscous to limit problems of devitrification. The
content of SiO.sub.2 is limited to 68% insofar as the greater the
content of SiO.sub.2, the greater the high-temperature viscosity of
the glass, and thus the glass is more difficult to melt.
Al.sub.2O.sub.3 (17%-21%): the presence of ZnO and of MgO at the
specified (rather large) quantities makes it critical to control
the content of Al.sub.2O.sub.3 in order to limit devitrification
phenomena. Excessive quantities of Al.sub.2O.sub.3 (>21%) make
the composition more likely to devitrify (into mullite crystals or
others) (see comparative example 15), which is not desirable.
Conversely, quantities of Al.sub.2O.sub.3 that are too small
(<17%) are unfavorable to nucleation and to the formation of
small .beta.-quartz crystallites. An Al.sub.2O.sub.3 content in the
range 17.5% to 19% (bounds included) is advantageous. Li.sub.2O (1%
to <2%): the inventors have found that it is possible to obtain
glass-ceramics satisfying the requirements of the above
specifications while limiting the content of Li.sub.2O to less than
2% (and thus substantially limiting said content). Said content is
advantageously at most 1.9% (.ltoreq.1.9%). The minimum quantity of
1% is nevertheless necessary in order to obtain a material that is
transparent, to keep a low high-temperature viscosity, and to keep
satisfactory devitrification characteristics. This minimum quantity
is advantageously 1.5%. Thus, a Li.sub.2O content in the range 1.5%
to 1.9% (bounds included) is most particularly preferred. MgO (1%
to 4%) and ZnO (1% to 6%): the inventors have obtained the
looked-for result by making joint use of these two elements, in the
specified quantities, as partial substitutes for Li.sub.2O (present
from 1% to less than 2%).
MgO: this element decreases high-temperature viscosity. It forms
part of the solid solution of .beta.-quartz. It has less impact on
devitrification than ZnO (see below), but it greatly increases the
CTE of the glass-ceramics (see comparative example 18). That is why
its content should lie in the range 1% to 4%, advantageously in the
range 1% to 3%.
ZnO: this element also serves to reduce the high-temperature
viscosity of the glass and also forms part of the solid solution of
.beta.-quartz. Compared with Li.sub.2O, it increases the CTE of the
glass-ceramic, but it does so only moderately, thus making it
possible to obtain glass-ceramics with CTE values less than
2510.sup.-7K.sup.-1, or indeed less than 2010.sup.-7K.sup.-1. When
present in too great a quantity, it gives rise to unacceptable
devitrification. In preferred manner, its content lies in the range
1% to 4%, and in very preferred manner in the range 3% to 4%.
TiO.sub.2 (1% to 5%) and ZrO.sub.2 (0 to 2%): ZrO.sub.2 is
opportunely (but not compulsorily) present. In reference to its
efficiency, when it is present, it has generally to be present at
levels of at least 0.1%. Otherwise stated, ZrO.sub.2 is "not
present" or is efficiently present, generally at a level in the
range 0.1 to 2%. These elements, TiO.sub.2 and ZrO.sub.2, enable
the glass to nucleate and enable a transparent glass-ceramic to be
formed. The joint presence of these two elements makes it possible
to optimize nucleation. Too great a content of TiO.sub.2 makes it
difficult to obtain a transparent glass-ceramic. TiO.sub.2 is
advantageously present at a content lying in the range 2% to 4%.
Too great a content of ZrO.sub.2 leads to unacceptable
devitrification. ZrO.sub.2 is advantageously present at a content
lying in the range 0.5% to 2%, very advantageously it is present at
a content lying in the range 1% to 2%. BaO (0 to 4%), SrO (0 to
4%), CaO (0 to 1%), Na.sub.2O (0 to 1%), and K.sub.2O (0 to 1%):
these elements are optionally present. To have an effect, each of
said elements, when it is present, is generally present at levels
of at least 100 ppm. Otherwise stated, BaO is "not present" or is
efficiently present, generally at a level in the range 0.01 to 4%;
SrO is "not present" or is efficiently present, generally at a
level in the range 0.01 to 4% (see however later); CaO is "not
present" or is efficiently present, generally at a level in the
range 0.01 to 1%; Na.sub.2O is "not present" or is efficiently
present, generally at a level in the range 0.01 to 1%; and K.sub.2O
is "not present" or is efficiently present, generally at a level in
the range 0.01 to 1%. These elements remain in the residual glass
after crystallization. They reduce the viscosity of the glass at
high temperature, they facilitate dissolution of the ZrO.sub.2
(when it is present) and they limit devitrification into mullite,
but they also increase the CTE of the glass-ceramics. That is why
the sum of these elements must be equal to or less than 6%. It may
be observed that SrO is generally not present as an added raw
material, given that it is an expensive material. In such a context
(SrO not present as added raw material), if SrO is present, it is
only present as inevitable traces (<100 ppm), brought in as an
impurity with at least one of the raw materials used or in the
cullet used. Fining agents: the composition of the glass-ceramics
advantageously includes at least one fining agent comprising
SnO.sub.2. When present, said at least one fining agent is present
at an effective quantity (for performing chemical fining), which
conventionally does not exceed 2% by weight. It is thus generally
present in the range 0.05% to 2% by weight.
In a particularly opportune manner, for environmental reasons,
fining is obtained by using SnO.sub.2--generally with 0.05% to 0.6%
by weight of SnO.sub.2, and more particularly with 0.15% to 0.4% by
weight of SnO.sub.2--within the composition of the glass-ceramics
of the present application which contains neither As.sub.2O.sub.3
nor Sb.sub.2O.sub.3, or which contains only inevitable traces of at
least one of these toxic compounds
(As.sub.2O.sub.3+Sb.sub.2O.sub.3<1000 ppm). If traces of at
least one of these compounds are present, they are present as
contamination; by way of example, this may be due to the presence
of recycled materials of the cullet type (derived from old
glass-ceramics fined with these compounds) in the charge of raw
materials able to vitrify. Under such circumstances, the
co-presence of at least one other fining agent, such as CeO.sub.2,
a chloride, and/or a fluoride is not excluded but, preferably,
SnO.sub.2 is present as the single fining agent.
It should be observed that the absence of an effective quantity of
chemical fining agent(s), or indeed the absence of any chemical
fining agent, is not completely to be excluded; fining can then be
performed thermally. This non-excluded variant is nevertheless not
preferred in any way. Coloring agents: the composition of the
glass-ceramics advantageously includes at least one coloring agent.
Ii is above mentioned that in the context of cooktops, it is
appropriate to mask elements that are arranged under said cooktops.
Said at least one coloring agent is present in an effective amount
(generally at at least 0.01% by weight), it is conventionally
present at levels of at most 2% by weight, or indeed at levels of
at most 1% by weight. Said at least one coloring agent is
conventionally selected from oxides of transition elements (e.g.,
V.sub.2O.sub.5, CoO, Cr.sub.2O.sub.3, Fe.sub.2O.sub.3 (see below),
NiO, . . . ) and of rare earths (e.g., Nd.sub.2O.sub.3,
Er.sub.2O.sub.3, . . . ). In preferred manner, vanadium oxide
V.sub.2O.sub.5 is used since said vanadium oxide leads to low
absorption in the glass, which is advantageous for melting. The
absorption, it makes possible, is generated during the ceramming
treatment (during which it is partially reduced). It is
particularly advantageous to combine V.sub.2O.sub.5 with other
coloring agents such as Cr.sub.2O.sub.3, CoO, or Fe.sub.2O.sub.3
(see below), since that enables transmission to be modulated. The
inventors have observed that by reducing the Li.sub.2O content,
smaller quantities of V.sub.2O.sub.5 are needed for obtaining the
same coloring, which is also advantageous from a cost point of view
(since V.sub.2O.sub.5 is an element that is quite expensive). With
reference to the requirements set out below (formulated for the
utilization thickness, typically in the range 1 mm to 8 mm, more
generally in the range 2 mm to 5 mm, and often 4 mm): to have an
integrated transmission (TL) less than 10%, preferably less than
4%; while maintaining transmission:
+ at 625 nanometers (nm) (T.sub.625 nm) greater than 1%, thus
making it possible to pass light, for display purposes, from an LED
emitting in the red and placed under the plate (cooktop),
+ at 950 nanometers (nm) (T.sub.950 nm) lying in the range 50 to
75%, thus enabling infra-red electronic touch controls to be used,
which emit and receive at said wavelength,
the combination (weight % relative to the total composition) of
coloring agents as set out below has been found to be particularly
advantageous:
TABLE-US-00001 V.sub.2O.sub.5 0.005% to 0.1% Fe.sub.2O.sub.3 0.01%
to 0.32% Cr.sub.2O.sub.3 0 to 0.1% CoO 0 to 0.1%.
Among the coloring agents, Fe.sub.2O.sub.3 has a special place. It
has an effect on color and it is actually often present, in a less
or more important amount, as an impurity (e.g. coming from the raw
materials). It is however not excluded to add some Fe.sub.2O.sub.3
to adjust the color. Its acceptable presence "in large quantity" in
the composition of glass-ceramics of the present application makes
it possible to use raw materials that are less pure and thus often
less expensive.
The above-identified ingredients involved, or potentially involved,
in the composition of glass-ceramics of the present application
(SiO.sub.2, Al.sub.2O.sub.3, Li.sub.2O, MgO, ZnO, TiO.sub.2,
ZrO.sub.2, BaO, SrO, CaO, Na.sub.2O, K.sub.2O, fining agent(s)
(comprising SnO.sub.2), and coloring agent(s)) can indeed represent
100% by weight of the composition of glass-ceramics of the present
application, but, a priori; the presence of at least one other
compound is not to be totally excluded, providing it is at low
quantity (generally less than or equal to 3% by weight) and does
not substantially affect the properties of the glass-ceramics. In
particular, the following compounds may be present, at a total
content of less than or equal to 3% by weight, each of them being
present at a total content less than or equal to 2% by weight:
P.sub.2O.sub.5, B.sub.2O.sub.3, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5,
WO.sub.3, and MoO.sub.3.
The above-identified ingredients involved, or potentially involved,
in the composition of glass-ceramics of the present application
(SiO.sub.2, Al.sub.2O.sub.3, Li.sub.2O, MgO, ZnO, TiO.sub.2,
ZrO.sub.2, BaO, SrO, CaO, Na.sub.2O, K.sub.2O, fining agent(s)
(comprising SnO.sub.2), and coloring agent(s)), thus represent at
least 97% by weight, or indeed at least 98% by weight, or indeed at
least 99% by weight, or even 100% by weight (see above) of the
composition of glass-ceramics of the present application.
The glass-ceramics of the present application thus contain
SiO.sub.2, Al.sub.2O.sub.3, Li.sub.2O, ZnO, and MgO as essential
ingredients for the solid solution of (.beta.-quartz (see below).
This solid solution of .beta.-quartz represents the main
crystalline phase. This solid solution of .beta.-quartz generally
represents more than 80% by weight of the total crystallized
fraction. It generally represents more than 90% by weight of said
total crystallized fraction. The size of the crystals is small
(typically less than 70 nm), which enables the glass-ceramics to be
transparent (integrated transmission .gtoreq.1% and diffusion
<2%).
Glass-ceramics of the present application contain about 10% to
about 40% by weight of residual glass.
In a second aspect, the present application provides articles that
are constituted at least in part of a glass-ceramic of the present
application as described above. Said articles are optionally
constituted in full out of a glass-ceramic of the present
application. Said articles advantageously consist of cooktops,
which are a priori bulk colored (see above). Nevertheless, that is
not the only application for which they can be used. In particular,
they also may constitute the material constituting cooking
utensils, microwave oven plates, oven doors, whether colored or
not. It will naturally be understood that the glass-ceramics of the
present application are logically used in contexts that are
compatible with their CTEs. Thus, cooktops are strongly recommended
for use with induction heating means, particularly with induction
heating means associated with infrared sensors.
In a third aspect, the present application provides aluminosilicate
glasses that are precursors for the glass-ceramics of the present
application, as described above. In characteristic manner, said
glasses present a composition that makes it possible to obtain said
glass-ceramics. Said glasses generally present a composition
corresponding to that of said glass-ceramics, but the
correspondence is not necessarily complete insofar as the person
skilled in the art readily understands that the heat treatments
applied to such glasses for obtaining glass-ceramics are likely to
have some effect on the composition of the material. The glasses of
the present application are obtained in conventional manner by
melting a charge of raw materials able to vitrify (raw materials
making them up being present in the appropriate proportions).
Nevertheless, it can be understood (and will not surprise the
person skilled in the art) that the charge in question may contain
cullet. Said glasses are particularly interesting in that: they
have advantageous devitrification properties, in particular
compatible with using forming methods involving rolling, floating,
and pressing. Said glasses present a low liquidus temperature
(<1400.degree. C.), and a high viscosity at liquidus (>200
Pas, indeed >400 Pas, preferably >500 Pas); and/or,
advantageously, and they have a low viscosity at high temperature
(T.sub.30 Pas<1640.degree. C.).
In other respects, it has to be noted that it is possible to obtain
(from said precursor glasses) the glass-ceramics of the present
application by performing ceramming (crystallization) thermal
cycling of short duration (less than 3 h), preferably of very short
duration (less than 1 h); and that the resistivity of said
precursor glasses is low (resistivity less than 50 .OMEGA.cm,
preferably less than 20 .OMEGA.cm, at a viscosity of 30 Pas).
The low liquidus temperature, the high viscosity at liquidus, and
the low viscosity at high temperature (see above) are particularly
important.
In its last aspect, the present application provides a method of
preparing an article constituted at least in part of a
glass-ceramic of the present application, as described above.
Said method is a method by analogy.
In conventional manner, said method comprises heat treatment of a
charge of raw materials able to vitrify (it being understood that
such a charge able to vitrify may contain cullet (see above)) under
conditions that ensure melting and fining in succession, followed
by shaping the fined molten precursor glass (said shaping possibly
being performed by rolling, by pressing, or by floating), followed
by ceramming (or crystallization) heat treatment of the shaped
fined molten precursor glass. The ceramming heat treatment
generally comprises two steps: a nucleation step and another step
of growing crystals of the solid solution of .beta.-quartz.
Nucleation generally takes place in the temperature range
650.degree. C. to 830.degree. C. and crystal growth in the
temperature range 850.degree. C. to 950.degree. C. Concerning the
duration of each of these steps, mention may be made in entirely
non-limiting manner of about 5 minutes (min) to 60 min for
nucleation and about 5 min to 30 min for growth of crystals. The
person skilled in the art knows how to optimize the temperatures
and the durations of these two steps as a function of the
composition of the precursor glasses, in reference more
particularly to the aimed transparency.
Said method of preparing an article, constituted at least in part
of a glass-ceramic of the present application thus comprises in
succession: melting a charge of raw materials able to vitrify,
followed by fining the resulting molten glass; cooling the
resulting fined molten glass and simultaneously shaping it to the
shape desired for the intended article; and applying ceramming heat
treatment to said shaped glass.
The two successive steps of obtaining a shaped fined glass
(precursor of the glass-ceramic) and ceramming said shaped fined
glass may be performed immediately one after the other, or they may
be spaced apart in time (on a single site or on different
sites).
In characteristic manner, the charge of raw materials able to
vitrify has a composition that makes it possible to obtain a
glass-ceramic of the present application, thus having the
composition by weight as specified above (advantageously including
SnO.sub.2 as a fining agent (in the absence of As.sub.2O.sub.3 and
Sb.sub.2O.sub.3), preferably as the single fining agent). The
ceramming performed on the glass obtained from such a charge is
entirely conventional. It is mentioned above that said ceramming
may be obtained in a short length of time (<3 h), or indeed in a
very short length of time (<1 h).
In the context of preparing an article, such as a cooktop, the
precursor glass is cut after being shaped and prior to being
subjected to the ceramming treatment (ceramming cycle). It is
generally also edged, rounded shaped and decorated. Such forming
and decorating steps may be performed before or after the ceramming
heat treatment. By way of example, the decorating may be performed
by screen-printing.
The present application is illustrated below by the following
examples and comparative examples.
EXAMPLES
To produce batches of 1 kilogram (kg) of precursor glass, the raw
materials, in the proportions specified in the first portion of the
table below (proportions expressed by (weight % of) oxides) (which
table is spread over several pages), were mixed together
carefully.
The mixtures were placed for melting in crucibles made of platinum.
The crucibles containing said mixtures were then placed in a oven
preheated to 1550.degree. C. They were subjected therein to a
melting cycle of the following type: temperature rise from
1550.degree. C. to 1670.degree. C. in 1 h; temperature maintained
at 1670.degree. C. for 5 h 30.
The crucibles were then extracted from the oven and the molten
glass was poured onto a preheated steel plate. It was rolled on the
plate to a thickness of 6 mm. Glass plates were thus obtained. They
were annealed at 650.degree. C. for 1 h and subsequently cooled
down slowly. The properties of the resulting glasses are given in
the second portion of the table below.
Viscosities were measured using a rotational viscosimeter
(Gero).
T.sub.30 Pas (.degree. C.) corresponds to the temperature at which
the viscosity of the glass was 30 Pas.
The resistivity of the glass was measured at high temperature, on a
thickness of 1 centimeter (cm) of molten glass, using a 4-point
contact RLC bridge. The table gives the resistivity measured at the
temperature at which the viscosity was 30 Pas.
T.sub.liq (.degree. C.) is the liquidus temperature. The liquidus
is given by a range of associated temperatures and viscosities: the
highest temperature corresponds to the minimum temperature at which
no crystal was observed, the lowest temperature corresponds to the
maximum temperature at which crystals were observed.
The devitrification characteristics were determined as follows. 0.5
cubic centimeter (cm.sup.3) samples of glass were subjected to the
following heat treatment: placing in a oven preheated to
1430.degree. C.; maintaining this temperature for 30 min; lowering
to the test temperature, T, at a rate of 10.degree. C./min;
maintaining this temperature for 17 h; and quenching the
samples.
The crystals present, if any, were observed by optical microscopy.
The ceramming cycle performed was as follows: rapid temperature
rise up to 500.degree. C.; temperature rise from 500.degree. C. to
650.degree. C. at a heating rate of 23.degree. C./min; temperature
rise from 650.degree. C. to 820.degree. C. at a heating rate of
6.7.degree. C./min; temperature rise from 820.degree. C. to the
maximum temperature Tmax (specified in the table) at a rate of
15.degree. C./min; maintaining this temperature Tmax for 7 min (in
all of the examples except example 18 (comparative example, see
below) with the ceramming treatment Ceram 1); cooling down to
850.degree. C. at 35.degree. C./min; and cooling down to ambient
temperature as a function of the inertia of the oven.
For certain examples (examples 1, 2, 4, 18 and 20) the results are
given as obtained at the end of two different ceramming treatments
(Ceram 1 and Ceram 2, which differ in the value of their Tmax).
The ceramming cycle Ceram 1 of example 18 (Tmax=830.degree. C.)
does not actually correspond to the "general" ceramming cycle
specified above. It was as follows: temperature rise up to
710.degree. C. at a heating rate of 22.5.degree. C./min;
temperature maintained at 710.degree. C. for 60 min; temperature
rise from 710.degree. C. to 830.degree. C. at a heating rate of
24.degree. C./min; temperature maintained at 830.degree. C. for 30
min; and cooling to ambient temperature as a function of the
inertia of the oven. The properties of the glass-ceramics obtained
are given in the last portion of Table 1 below.
These glass-ceramics contain a solid solution of .beta.-quartz as
the main crystalline phase (as verified by X-ray diffraction) (with
the exception of that of comparative example 16). Thus, the
glass-ceramics of examples 5 and 6 respectively contain 96% and 95%
(wt. %) of solid solution of .beta.-quartz phase (relative to the
total crystallized fraction) and the mean sizes of their
.beta.-quartz crystals respectively were 46 nm and 43 nm. The
percentage of .beta.-quartz solid solution and the mean sizes of
the crystals were determined by the Rietveld method.
The CTE (coefficients of thermal expansion (from ambient
temperature (25.degree. C.) to 300.degree. C.
(CTE.sub.25-300.degree. C.) were measured on bar-shaped
glass-ceramic samples with a high-temperature dilatometer (DIL
402C, Netzsch) at a heating rate of 3.degree. C./min.
The aspect of the samples (transparency, color) is given in the
table.
For some samples, total and diffuse transmission measurements were
carried out at 4 mm using a Varian spectrophotometer (model Cary
500 Scan), fitted with an integrating sphere. On the basis of these
measurements, the integrated transmission (TL (%)) in the visible
range (between 380 and 780 nm) and the diffusion percentage
(Diffusion (%)) were calculated in application of the standard ASTM
D 1003-13 (with D65 illuminant and 2.degree. observer).
Transmission values (at 625 nm (T.sub.625 nm), at 950 nm (T.sub.950
nm)) are also specified for some samples. Examples 1 to 14 in the
table illustrate the present application. Examples 1 to 4 are
preferred because of the values for the liquidus viscosity of the
precursor glasses.
Examples 15 to 21 (of the table) are comparative examples.
In example 15, the Al.sub.2O.sub.3 content is too high
(21.48%>21%) and the observed devitrification of the glass is
unacceptable (said glass does not have the required
properties).
In example 16, the Li.sub.2O and Al.sub.2O.sub.3 contents are too
small and the Na.sub.2O+K.sub.2O+BaO+CaO content is too large. Only
a small quantity of crystals formed during the heat treatment and
they were spinel crystals and not a solid solution of
.beta.-quartz. Consequently, the CTE after ceramming was too
high.
In example 17, the Li.sub.2O, Al.sub.2O.sub.3, and ZnO contents are
too large, the SiO.sub.2 content is too small. Consequently, the
glass possesses devitrification characteristics that are
unacceptable.
In example 18, the MgO content is too large, and consequently the
CTE of the glass-ceramics is too high.
In example 19, the MgO content is too small and the ZnO content is
large. Consequently, the liquidus temperature is very high and the
viscosity at the liquidus is too low (the glass does not have the
required properties).
In example 20, the ZnO content is too small and the MgO content is
high. Consequently, the CTE of the glass-ceramic is too high or the
glass-ceramic shows optical properties that are unacceptable.
In example 21, the ZnO content is too high. Consequently, the
high-temperature viscosity of the glass is very low and the
liquidus temperature is high, so the viscosity at the liquidus is
too small (the glass does not have the required properties).
TABLE-US-00002 TABLE Examples (wt %) 1 2 3 4 5 SiO.sub.2 66.71
66.61 66.51 65.97 64.10 Al.sub.2O.sub.3 18.10 18.10 18.10 18.89
19.72 Li.sub.2O 1.63 1.63 1.63 1.62 1.86 MgO 2.17 2.17 2.17 2.16
2.47 ZnO 3.08 3.08 3.08 3.07 3.56 BaO 2.47 2.47 2.47 2.46 2.46 CaO
0.44 0.44 0.44 0.44 0.44 TiO.sub.2 2.99 2.80 2.62 2.98 2.98
ZrO.sub.2 1.33 1.62 1.90 1.33 1.33 Na.sub.2O 0.61 0.61 0.61 0.61
0.61 K.sub.2O SnO.sub.2 0.30 0.30 0.30 0.30 0.30 Fe.sub.2O.sub.3
0.12 0.12 0.12 0.12 0.12 V.sub.2O.sub.5 0.03 0.03 0.03 0.03 0.03
Cr.sub.2O.sub.3 0.02 0.02 0.02 0.02 0.02 CoO Na.sub.2O + K.sub.2O +
BaO + CaO + SrO 3.53 3.53 3.53 3.51 3.51 T.sub.30 Pa s (.degree.
C.) 1636 1621 1619 1628 1571 T.sub.liq (.degree. C.) 1350-1366
1338-1350 1350-1366 1350-1360 1350-1372 Viscosity at T.sub.liq
600-800 700-850 500-650 600-700 300-450 (Pa s) Crystalline phase
spinel zircon + spinel zircon spinel spinel that devitrifies at the
liquidus temperature Resistivity at 8.4 9.4 9.9 8.8 7.9 30 Pa s
(.OMEGA. cm) Ceram 1 Tmax (.degree. C.) 890 900 890 880 880 Aspect
transparent transparent transparent transparent transparent colored
colored colored colored colored CTE.sub.25-300.degree. C. 18.4 17.6
19.7 20 17.5 (.times.10.sup.-7 K.sup.-1) Ceram 2 Tmax (.degree. C.)
920 920 920 Aspect transparent transparent transparent colored
colored colored CTE.sub.25-300.degree. C. 17.5 16.3 18.3
(.times.10.sup.-7 K.sup.-1) TL (%) 1 3 Diffusion (%) 1.5 1
T.sub.625 nm (%) 3.1 8.3 T.sub.950 nm (%) 58 64 Examples (wt %) 6 7
8 9 SiO.sub.2 63.70 65.34 65.65 65.45 Al.sub.2O.sub.3 19.60 19.67
19.79 17.99 Li.sub.2O 1.84 1.62 1.63 1.62 MgO 1.85 2.15 2.78 2.15
ZnO 4.77 3.06 1.84 3.06 BaO 2.45 2.46 2.47 3.48 CaO 0.44 0.44 0.44
0.63 TiO.sub.2 2.96 2.97 2.99 2.97 ZrO.sub.2 1.32 1.32 1.33 1.32
Na.sub.2O 0.61 0.61 0.61 0.86 K.sub.2O SnO.sub.2 0.29 0.30 0.30
0.30 Fe.sub.2O.sub.3 0.12 0.01 0.12 0.12 V.sub.2O.sub.5 0.03 0.03
0.03 0.03 Cr.sub.2O.sub.3 0.02 0.02 0.02 0.02 CoO Na.sub.2O +
K.sub.2O + BaO + CaO + SrO 3.50 3.51 3.53 4.97 T.sub.30 Pa s
(.degree. C.) 1584 1621 1604 1632 T.sub.liq (.degree. C.) 1370-1387
1350-1373 1350-1367 Viscosity at T.sub.liq 250-350 500-700 500-600
(Pa s) Crystalline phase spinel mullite + spinel mullite that
devitrifies at the liquidus temperature Resistivity at 8.1 7.8 9.9
30 Pa s (.OMEGA. cm) Ceram 1 Tmax (.degree. C.) 880 880 890 920
Aspect transparent transparent transparent transparent colored
colored colored colored CTE.sub.25-300.degree. C. 15.8 21.3 22.4
20.2 (.times.10.sup.-7 K.sup.-1) Ceram 2 Tmax (.degree. C.) Aspect
CTE.sub.25-300.degree. C. (.times.10.sup.-7 K.sup.-1) TL (%)
Diffusion (%) Examples (wt %) 10 11 12 13 14 SiO.sub.2 66.14 67.57
67.85 63.86 63.86 Al.sub.2O.sub.3 18.10 18.98 18.87 19.00 19.00
Li.sub.2O 1.63 1.28 1.84 1.84 1.84 MgO 2.17 2.49 1.75 1.75 1.75 ZnO
3.08 4.94 4.95 4.95 4.95 BaO 2.47 0.00 0.00 2.50 2.50 CaO 0.44 0.00
0.00 0.44 0.44 TiO.sub.2 2.99 2.62 2.63 3.02 2.62 ZrO.sub.2 1.90
1.75 1.75 1.35 1.75 Na.sub.2O 0.61 0.00 0.00 0.62 0.62 K.sub.2O
0.25 0.25 SnO.sub.2 0.30 0.30 0.30 0.28 0.28 Fe.sub.2O.sub.3 0.12
0.03 0.03 0.09 0.09 V.sub.2O.sub.5 0.03 0.04 0.03 0.03 0.03
Cr.sub.2O.sub.3 0.02 0.00 0.00 0.00 0.00 CoO 0.02 0.02 Na.sub.2O +
K.sub.2O + BaO + SrO + CaO 3.53 0.00 0.00 3.81 3.81 T.sub.30 Pa s
(.degree. C.) 1635 1610 1617 1581 T.sub.liq (.degree. C.) 1350-1366
1350-1375 1350-1375 1328-1353 1325-1355 Viscosity at T.sub.liq
600-750 450-650 450-650 450-700 (Pa s) Crystalline phase zircon +
spinel mullite + spinel zircon + spinel that devitrifies at the
liquidus temperature Resistivity at 8.3 12 7.8 30 Pa s (.OMEGA. cm)
Ceram 1 Tmax (.degree. C.) 890 975 975 880 855 Aspect transparent
transparent transparent transparent transparent colored colored
colored colored colored CTE.sub.25-300.degree. C. 24.7 18.1 7.8 13
12.9 (.times.10.sup.-7 K.sup.-1) Ceram 2 Tmax (.degree. C.) Aspect
CTE.sub.25-300.degree. C. (.times.10.sup.-7 K.sup.-1) TL (%)
Diffusion (%) Comparative examples (wt %) 15 16 17 18 SiO.sub.2
63.55 65.81 54.21 63.03 Al.sub.2O.sub.3 21.48 14.57 25.50 20.00
Li.sub.2O 1.60 0.49 2.70 1.84 MgO 2.13 1.33 1.00 4.95 ZnO 3.04 4.70
7.70 1.75 BaO 2.44 6.24 1.00 2.50 CaO 0.44 0.99 1.30 0.45 TiO.sub.2
2.95 2.89 4.10 3.02 ZrO.sub.2 1.31 1.28 2.00 1.35 Na.sub.2O 0.60
1.01 0.62 K.sub.2O 0.21 SnO.sub.2 0.29 0.29 0.30 0.30
Fe.sub.2O.sub.3 0.12 0.13 0.13 0.13 V.sub.2O.sub.5 0.03 0.04 0.04
0.04 Cr.sub.2O.sub.3 0.02 0.02 0.02 0.02 CoO Na.sub.2O + K.sub.2O +
BaO + SrO + CaO 3.48 8.45 2.30 3.57 T.sub.30 Pa s (.degree. C.)
1587 1705 1421 T.sub.liq (.degree. C.) >1400 >1370 Viscosity
at T.sub.liq <200 <100 (Pa s) Crystalline phase mullite that
devitrifies at the liquidus temperature Resistivity at 10.5 22.3
7.6 30 Pa s (.OMEGA. cm) Ceram 1 Tmax (.degree. C.) 930 920 830
Aspect transparent transparent transparent colored colored colored
CTE.sub.25-300.degree. C. 38.1 14.9 25.8 (.times.10.sup.-7
K.sup.-1) Ceram 2 Tmax (.degree. C.) 850 Aspect opalescent
CTE.sub.25-300.degree. C. (.times.10.sup.-7 K.sup.-1) TL (%)
Diffusion (%) Comparative Examples (wt %) 19 20 21 SiO.sub.2 62.31
66.78 62.17 Al.sub.2O.sub.3 19.93 18.13 18.33 Li.sub.2O 1.80 1.63
1.51 MgO 0.47 2.91 1.83 ZnO 5.86 0.49 6.90 BaO 3.53 3.53 2.42 CaO
0.64 0.53 0.44 TiO.sub.2 2.90 3.00 3.28 ZrO.sub.2 1.29 1.34 1.84
Na.sub.2O 0.59 0.95 0.60 K.sub.2O 0.21 0.22 0.21 SnO.sub.2 0.29
0.30 0.29 Fe.sub.2O.sub.3 0.12 0.13 0.12 V.sub.2O.sub.5 0.04 0.04
0.04 Cr.sub.2O.sub.3 0.02 0.02 0.02 CoO Na.sub.2O + K.sub.2O + BaO
+ SrO + CaO 4.97 5.23 3.68 T.sub.30 Pa s (.degree. C.) 1580 1658
1561 T.sub.liq (.degree. C.) 1402-1415 1386-1402 Viscosity at
T.sub.liq 170-210 160-200 (Pa s) Crystalline phase spinel spinel
that devitrifies at the liquidus temperature Resistivity at 9.7 7.2
9.3 30 Pa s (.OMEGA. cm) Ceram 1 Tmax (.degree. C.) 890 Aspect
transparent colored CTE.sub.25-300.degree. C. 30.2
(.times.10.sup.-7 K.sup.-1) Ceram 2 Tmax (.degree. C.) 920 Aspect
opalescent colored CTE.sub.25-300.degree. C. 24.8 (.times.10.sup.-7
K.sup.-1) TL (%) 0.3 Diffusion (%) 8 T.sub.625 nm (%) 1.2
* * * * *